System for recovery of lithium from a geothermal brine

ABSTRACT

This invention relates generally to a system and process for recovery of select minerals and lithium from a geothermal brine. The system and process are configured for the sequential recovery of zinc, manganese, and lithium from a Salton Sea Known Geothermal Resource Area brine. The system and process includes: 1) an impurity removal circuit; then 2) a continuous counter-current ion exchange (CCIX) circuit for selectively recovering lithium chloride from the brine flow and concentrating it using a CCIX unit; and then 3) a lithium chloride conversion circuit for converting lithium chloride to lithium carbonate or lithium hydroxide product.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 16/010,286 filed on Jun. 15, 2018, which claims the benefit ofU.S. Provisional Patent Application No. 62/520,024 filed on Jun. 15,2017 and U.S. Provisional Patent Application No. 62/671,489 filed on May15, 2018. This application incorporates each of said applications byreference into this document as if fully set out at this point.

BACKGROUND OF THE INVENTION 1. Field of the Invention

This invention relates generally to a system and process for recovery oflithium from a geothermal brine, and more particularly to a system andsequential process for recovery of zinc, manganese, lithium or acombination thereof from a Salton Sea Known Geothermal Resource Areabrine.

2. Description of the Related Art

Salton Sea Known Geothermal Resource Area is located in the SaltonTrough, a major trans-tensional rift between the Pacific plate, on thewest, and the North American plate, on the east, which merges southwardthrough Mexico into the long, narrow Gulf of California.

The Salton Sea Known Geothermal Resource Area has the most geothermalcapacity potential in the U.S. Geothermal energy, the harnessing of heatradiating from the Earth's crust, is a renewable resource that iscapable of cost-effectively generating large amounts of power. Inaddition, the Salton Sea Known Geothermal Resource Area is one of NorthAmerica's prime sources of alkali metals, alkaline earth metals andtransition metals, such as lithium, potassium, rubidium, iron, zinc andmanganese.

Brines from the Salton Sea Known Geothermal Resource Area are unusuallyhot (up to at least 390° C. at 2 km depth), hypersaline (up to 26 wt.%), and metalliferous (iron (Fe), zinc (Zn), lead (Pb), copper (Cu)).The brines are primarily sodium (Na), potassium (K), calcium (Ca)chlorides with up to 25 percent of total dissolved solids; they alsocontain high concentrations of metals such as Fe, Mn, Li, Zn, and Pb.While the chemistry and high temperature of the Salton Sea brines haveled to the principal challenges to the development of the Salton SeaKnown Geothermal Resource Area, lithium and these rare earth elementstypically maintain high commodity value and are used in a range ofspecialized industrial and technological applications.

It is therefore desirable to provide an improved system and process forrecovery of lithium from a geothermal brine.

It is further desirable to provide a system and process for recovery oflithium from a Salton Sea Known Geothermal Resource Area brine.

It is still further desirable to provide a system and sequential processfor recovery of zinc, manganese, lithium or a combination thereof from aSalton Sea Known Geothermal Resource Area brine.

It is still further desirable to provide a system and process forsequential recovery of zinc, manganese, and lithium from a Salton SeaKnown Geothermal Resource Area brine using impurity removal, selectiverecovery of lithium chloride, and selective conversion to lithiumcarbonate.

Before proceeding to a detailed description of the invention, however,it should be noted and remembered that the description of the inventionwhich follows, together with the accompanying drawings, should not beconstrued as limiting the invention to the examples (or embodiments)shown and described. This is so because those skilled in the art towhich the invention pertains will be able to devise other forms of thisinvention within the ambit of the appended claims.

SUMMARY OF THE INVENTION

In general, in a first aspect, the invention relates to a system forrecovery of lithium from a geothermal brine. The system has an impurityremoval circuit configured for selectively removing silica, iron andcertain metals from the geothermal brine (e.g., a Salton Sea KnownGeothermal Resource Area brine) to produce a polished brine. The systemalso has a continuous counter-current ion exchange circuit positioneddownstream of the impurity removal circuit. The continuouscounter-current ion exchange circuit is configured for selectivelyrecovering lithium chloride from the polished brine. The continuouscounter-current ion exchange circuit is further configured forconcentrating lithium chloride into a lithium chloride solution.Additionally, the system includes a lithium chloride conversion circuitpositioned downstream of the continuous counter-current ion exchangecircuit. The lithium chloride conversion circuit is configured forconverting lithium chloride in the lithium chloride solution to lithiumcarbonate or lithium hydroxide product.

The impurity removal circuit may include a first set of reaction tanksand a first clarifier positioned downstream of the first reaction tanks.The first clarifier is configured to selectively remove precipitatedsilica and iron from the geothermal brine to form a substantially ironand silica free brine. The impurity removal circuit may also include asecond set of reaction tanks positioned downstream of the firstclarifier and a second clarifier positioned downstream of the secondreaction tanks. The second clarifier is configure to selectively removeprecipitated metal oxides and/or hydroxides from the substantially ironand silica free brine to form a substantially zinc and manganese freebrine.

The system can also include a manganese and zinc solvent extractioncircuit positioned downstream of the impurity removal circuit andupstream of the continuous counter-current ion exchange circuit. Themanganese and zinc solvent extraction circuit may have a manganese zincextraction circuit with a zinc extraction stage having a first stagecontactor, a zinc scrubbing stage having a second stage contactor, and azinc stripping stage having a third stage contactor. Similarly,manganese and zinc solvent extraction circuit may have a manganesesolvent extraction circuit with a manganese extraction stage having afirst stage contactor, a manganese scrubbing stage having a second stagecontactor, and a manganese stripping stage having a third stagecontactor.

The continuous counter-current ion exchange circuit has a continuouscounter-current ion exchange lithium extraction unit with a plurality ofion exchange beds containing a lithium selective adsorbent. Thecontinuous counter-current ion exchange lithium extraction unit furtherincludes a plurality of sequential, individual process zones, with eachof the process zones having one or more ion adsorbent beds or columnsconfigured in parallel, in series, or in combinations of parallel andseries, flowing either in up flow or down flow modes. Fluid flow throughthe continuous counter-current ion exchange lithium extraction unit iscontrolled by pumping flow rates and a predetermined timing of arotating or indexing manifold valve system, creating a pseudo-simulatedmoving bed process where the exchange beds continually cycle through theindividual process zones. The lithium chloride selective absorbent maybe a manufactured resin-based alumina imbibed adsorbent, a lithiumalumina intercalates adsorbent, an alumina imbibed ion exchange resin,or an alumina-based adsorbent.

The lithium chloride conversion circuit can include a third set ofreaction tanks and a third clarifier positioned downstream of the thirdreaction tanks. The third clarifier is configured to selectively removeprecipitated calcium and magnesium from the lithium chloride solution toform a substantially calcium and magnesium free brine. The lithiumchloride conversion circuit can also include a boron ion exchangecircuit positioned downstream of the third clarifier, and the boron ionexchange is configured to selectively capture boron from thesubstantially calcium and magnesium free brine to form a substantiallycalcium, magnesium and/or boron free brine. Moreover, the lithiumchloride conversion circuit can include a divalent ion exchange circuitpositioned downstream of the boron ion exchange circuit. The divalention exchange is configured to selectively removing any remainingdivalent ions from the substantially calcium, magnesium and/or boronfree brine.

Furthermore, the lithium chloride conversion circuit may include alithium crystallization circuit configured to selectively convert thelithium chloride in the substantially calcium, magnesium and/or boronfree brine to lithium carbonate. Moreover, the lithium chlorideconversion circuit may include a solvent extraction and electrolysiscircuit configured to selectively convert the lithium chloride in thesubstantially calcium, magnesium and/or boron free brine to lithiumhydroxide.

The foregoing has outlined in broad terms some of the more importantfeatures of the invention disclosed herein so that the detaileddescription that follows may be more clearly understood, and so that thecontribution of the instant inventors to the art may be betterappreciated. The instant invention is not to be limited in itsapplication to the details of the construction and to the arrangementsof the components set forth in the following description or illustratedin the drawings. Rather, the invention is capable of other embodimentsand of being practiced and carried out in various other ways notspecifically enumerated herein. Finally, it should be understood thatthe phraseology and terminology employed herein are for the purpose ofdescription and should not be regarded as limiting, unless thespecification specifically so limits the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

These and further aspects of the invention are described in detail inthe following examples and accompanying drawings.

FIG. 1 is a process diagram of an example of a known crystallizerreactor clarifier process for power plant operations in the Salton SeaKnown Geothermal Resource Area;

FIG. 2 is a flow chart of an example of a process for recovery oflithium carbonate in accordance with an illustrative embodiment of theinvention disclosed herein;

FIG. 3 is a flow chart of an example of a process for recovery oflithium hydroxide in accordance with an illustrative embodiment of theinvention disclosed herein;

FIG. 4A is a process flow diagram of a system and process for recoveryof select minerals and lithium in accordance with an illustrativeembodiment of the invention disclosed herein;

FIG. 4B is a continuation of the process flow diagram shown in FIG. 4A;

FIG. 5 is a flow chart diagram of an example of a continuouscountercurrent ion exchange lithium recovery unit in accordance with anillustrative embodiment of the invention disclosed herein; and

FIG. 6 is a flow chart of an example of zinc and manganese solventextraction circuit in accordance with an illustrative embodiment of theinvention disclosed herein.

DETAILED DESCRIPTION OF THE INVENTION

While this invention is susceptible of embodiment in many differentforms, there is shown in the drawings, and will herein be describedhereinafter in detail, some specific embodiments of the instantinvention. It should be understood, however, that the present disclosureis to be considered an exemplification of the principles of theinvention and is not intended to limit the invention to the specificembodiments or algorithms so described.

This invention relates generally to a system and process for recovery oflithium from a geothermal brine, and more particularly to a system andsequential process for recovery of zinc, manganese, lithium or acombination thereof from a Salton Sea Known Geothermal Resource Area(“SSKGRA”) brine. The system and process includes: 1) impurity removal(silica and metals); 2) selectively recovering lithium chloride from thebrine flow and concentrating it using continuous counter-current ionexchange; and 3) lithium chloride conversion to lithium carbonateproduct (or lithium hydroxide).

A geothermal brine flow from production geothermal wells in the SaltonSea Known Geothermal Resource Area is flashed into steam to power aturbine generator to produce electricity. As part of the power plantoperations and processes (the “power plant operations”), scalingconstituents (mainly iron silicates and amorphous silica) areselectively removed to minimize scale formation from the brine on theplant equipment, vessel internals and associated piping beforeinjection. In geothermal brines from the SSKGRA, the concentration ofsalt exceeds the solubility when the geothermal brine is flashed toatmospheric pressure so dilution water is added to keep the injectedbrine slightly below saturation with respect to salt. From this point inthe power plant operations, the brine is routed to a series of reactorclarifiers to selectively reduce the concentration of silica in theinjected brine to levels near saturation. The clarifiers precipitatesilica, along with some iron, and lesser concentrations of arsenic,barium and lead, resulting in a polished geothermal brine suitable forreinjection into the SSKGRA via the power plant injection wells.

As generally illustrated in FIG. 1, existing power plant operations 1000involve a liquid brine flow from geothermal production wells 1012 thatis partially flashed into steam due to pressure losses as the liquidbrine makes its way up the production well casing. The two-phase mixtureof brine and steam is routed to a high-pressure separator 1014 where theliquid brine and high pressure steam are separated. High pressure steam1016 is routed from the separator 1014 to a centrifugal type steamscrubber (not shown) that removes brine carryover from the steam, andfrom there the scrubbed high pressure steam 1016 is routed to theturbine generator 1020. The liquid brine from the high-pressureseparator 1014 is flashed into a standard-pressure crystallizer 1022,and the standard pressure steam 1024 from the standard-pressurecrystallizer 1022 is passed through a steam scrubber (not shown) andthen the scrubbed standard pressure steam 1024 is routed to the turbine1020. Precipitated solids from the clarifiers are mixed with the brinein the standard-pressure crystallizer 1022 and contact with the scalingmaterials, which reduces the scaling tendency in brine significantly.

A brine slurry mixture from the standard-pressure crystallizer 1022 isflashed into a low-pressure crystallizer 1018. Low pressure steam 1025from the low-pressure crystallizer 1018 flows through a steam scrubber(not shown) and then either to a low-pressure turbine or to thelow-pressure side of a dual entry turbine 1020. The brine slurry mixtureis flashed to atmospheric pressure in an atmospheric flash tank 1026 andthen flows into the clarifiers.

A primary clarifier 1028 comprising an internally recirculating reactortype clarifier precipitates silica down to close to equilibrium valuesfor the various scaling constituents at the operating temperature of thebrine, e.g., approximately 229° F. Primary Clarifier Overflow (“PCO”)refers to the clarified brine flowing out of the primary clarifier 1028,and Primary Clarifier Underflow (“PCU”) refers to the slurry flowing outof the bottom of the primary clarifier 1028. The precipitated solids areflocculated and settled to the bottom of the primary clarifier tank1028. A relatively clear brine PCO passes from the primary clarifier1028 to a secondary clarifier 1030 that removes additional suspendedsolids from the brine. Secondary Clarifier Overflow (“SCO”) 1038 refersto the clarified brine flowing out of the secondary clarifier 1030, andSecondary Clarifier Underflow (“SCU”) refers to the slurry flowing outof the bottom of the secondary clarifier 1030.

Flocculent and scale inhibitor are added between the primary clarifier1028 and the secondary clarifier 1030 to enhance solids settling and toprevent the precipitation of radioactive alkaline earth salts. Thestable SCO 1038 from the secondary clarifier 1030 is pumped intoinjection wells 1032. A portion of the precipitated solids from the PCUand the SCU is recycled upstream to the standard-pressure crystallizer1022 as seed material 1034. Accumulated solids in both the primaryclarifier 1028 and the secondary clarifier 1030 are routed to ahorizontal belt filter (“HBF”) 1036 for solids removal.

The HBF 1036 separates liquid from the solids in the slurry from the PCUand the SCU. The liquid can be separated by vacuum and passes through afilter cloth that rests on top of the carrier belt. The first stage ofthe HBF is a pH 1.0 acid wash of the slurry with hydrochloric acid toremove any lead precipitates from the filter cake. The second stage is apH 9.5 condensate water wash to neutralize any residual acid in thefilter cake. The third stage of the HBF steam dries the filter cake. Thefilter cake is transported to a local landfill for disposal.

The silica and iron concentrations in the brine at the PCO, SCO andinjection wells of the power plant operations are summarized as followsin Table 1:

TABLE 1 Si as SiO₂ Fe As K Zn Mn Li Location (mg/kg) (mg/kg) (mg/kg)(mg/kg) (mg/kg) (mg/kg) (mg/kg) PCO 167 ± 25  1,579 ± 123 17.0 ± 4.020,600 ± 2,200 625 ± 42 1,705 ± 101 264 ± 24 SCO 159 ± 19 1,560 ± 8816.9 ± 4.0 20,600 ± 2,600 639 ± 41 1,693 ± 134 265 ± 23 Injection 160 ±19 1,557 ± 87 16.9 ± 4.0 20,400 ± 2,500 621 ± 45 1,696 ± 92  265 ± 22Wells

The polished brine 1038 that exits the SCO from the power plant 1000with reduced amounts of scaling constituents is well suited for mineralextraction, and rather than injecting the polished brine into theinjection well 1032, it is made immediately available to the inventivesystem and process 200 for recovery of lithium and/or other minerals.

The system and process 200 for recovery of minerals and lithium from ageothermal brine disclosed herein is further illustrated by thefollowing examples, which are provided for the purpose of demonstrationrather than limitation. An exemplary embodiment of the inventive systemand process 200 for recovery of lithium and/or other minerals generallyencompasses three sequential systems and processes: 1) an impurityremoval circuit 300; then 2) a continuous counter-current ion exchange(CCIX) circuit 400 for selectively recovering lithium chloride from thebrine flow and concentrating it using a CCIX unit 402; and then 3) alithium chloride conversion circuit 500 for converting lithium chlorideto lithium carbonate or lithium hydroxide product.

Recovery of Lithium Carbonate:

As illustrated in FIG. 2, a feed brine, such as a SSKGRA geothermalbrine or the brine 1038 that exits the SCO from the power plant 1000having reduced amounts of scaling constituents passes to the inventivesystem and process 200 for mineral and/or lithium extraction. The feedbrine is passed into the impurity removal circuit 300 having a first setof reaction tanks 302 and a tertiary clarifier 304 to remove iron andsilica followed by a second set of reaction tanks 306 and a finalclarifier 308 to remove manganese and zinc primarily. A first oriron/silica precipitation stage 300A of the impurity removal circuit 300includes adding limestone 310A and injecting air 310B into brine. Theair causes the iron to oxidize and the limestone slightly elevates thepH of the brine to counteract the oxidization of the iron by the air,which would otherwise reduce the pH of the brine. The tertiary clarifier304 is positioned downstream of the first reaction tank 302 to settleout the silica and iron in the brine. The precipitated solids aresettled to the bottom of the tertiary clarifier tank 304. The firststage 300A of the impurity removal circuit 300 reduces the ironconcentration in the brine overflow from about 1,600 part per million(ppm) down to less than about 5 ppm and reduces the silica concentrationin the brine overflow from about 60 ppm down to less than about 5 ppm. Arelatively clear brine overflow passes from the tertiary clarifier 304to a second or zinc/manganese precipitation stage 300B of impurityremoval circuit 300.

The second stage 300B of the impurity removal circuit 300 includesadding limestone 312A and lime 312B to the brine in the second reactiontank 306. This causes the brine pH to elevate to around 8. The finalclarifier 308 is positioned downstream of the second reaction tank 306and allows the metals as oxides and/or hydroxides (primarily zinc andmanganese) to settle. During the second stage 300B of the impurityremoval circuit 300, the manganese concentration in the brine is reducedfrom about 1700 ppm down to less than about 10 ppm, while zincconcentration is reduced about 600 ppm down to less than 5 ppm in thesecond stage 300B of the impurity removal circuit 300. Accumulatedsolids in the tertiary clarifier 304 and the final clarifier 308 arerespectively routed to a pneumapress filter HBF to prepare an Fe/Sifilter cake 314 and a Mn/Zn filter cake 316.

Acid is then added 318 to the brine from the final clarifier 308 toreduce the pH back down to between 4.5 and 6.0, with a brine temperaturebetween about 30° C. and about 100° C., which is suitable for thecontinuous countercurrent ion exchange (CCIX) circuit 400. The dissolvedsolids in the polished brine at this point in the process 100 compriseprimarily salts (as chlorides) with high concentrations of sodium,potassium, and calcium. The lithium concentration is comparatively lowat only ±250 parts per million (ppm).

The CCIX circuit 400 concentrates the lithium in the polished brine byapproximately 10 times and simultaneously separates the lithium from theother salts (calcium is of particular concern for downstreamoperations). The target result is a lithium chloride product stream 342(with some residual impurities) of around approximately 2,500 to 3,000ppm lithium. The residual brine is returned for reinjection into thegeothermal field through injection wells 320.

Referring now to FIG. 5, the CCIX circuit 400 includes a CCIX lithiumextraction unit 402 having a plurality of ion exchange beds containing alithium selective adsorbent (such as lithium alumina intercalates,alumina imbibed ion exchange resins), alumina-based adsorbents, and thelike) that are sequentially subjected to individual process zones (A, B,C, D) as part of the CCIX circuit 400. Each adsorption zone A, B, C, andD includes one or more ion adsorbent beds or columns configured inparallel, in series, or in combinations of parallel and series, flowingeither in up flow or down flow modes. Fluid flow is controlled bypumping flow rates and the timing of a rotating or indexing manifoldvalve system, creating a pseudo-simulated moving bed (SMB) process wherethe adsorption beds continually cycle through the individual processzones A, B, C and D.

The CCIX circuit 400 includes a series of sequential steps in a cyclicprocess. In order to eliminate the possibility of residual feed brineand brine salts from entering the elution zone D, which compriseslithium loaded adsorbent, largely unprocessed feed brine 411 isdisplaced from the adsorbent bed(s) of zone A using a portion of highlithium tenor product eluate 412 from zone D. The volume of displacementfluid drawn from zone D into zone A is at least enough to displace oneadsorbent bed void fraction during an index time (the time intervalbetween rotary valve indexes).

Then, brine feed 413 is introduced to the adsorbent bed(s) in zone Bwith a predetermined contact time sufficient to completely or almostcompletely exhaust the lithium selective adsorbent, and the depletedbrine exiting zone B is sent to raffinate 414. Zone B is sized such thatunder steady state operation nearly the complete mass transfer zone iscaptured within the zone and the steady state operation treats the brineso that the maximum lithium loading is achieved without significantlithium leaving with the lithium depleted raffinate as tails.

Next, a portion of raffinate 414 is introduced to zone C to displacelatent eluate solution 415, which is carried forward from zone D in thecyclic process, back to the inlet of zone D, the elution (strippingzone). The volume of displacement fluid drawn from zone B raffinate todisplace lithium eluant back into zone C is at least enough to displaceone adsorbent bed void fraction during the rotary valve index time.

Then, eluant 416 is introduced countercurrent to the adsorbent advanceto produce an enhanced lithium product stream 417. Eluant 416 compriseslow tenor lithium (as neutral salts, generally lithium chloride) inwater at a concentration from 0 to 1000 mg/L lithium and at temperaturesof 20° C. to 100° C. Properly tuned, the enhanced lithium product stream417 will have a lithium tenor 10- to 20-fold that of the eluant feed 416and greater than 99.8% rejection of brine hardness ions. The portion ofhigh tenor lithium eluant which displaces the largely untreated brinefrom zone C is enough fluid to completely displace brine salts from theadsorbent before the adsorbent enters zone D. This means that a portionof the high tenor eluate is introduced to the adsorption zone B.Depending on the tuning parameters, this recycled lithium could doublethe effective concentration of lithium entering the zone. This enhancedfeed tenor results in significantly increased lithium capacity andgreater lithium recovery efficiency.

An optional membrane separation 418 can be inserted into stream 417,which includes but is not limited to, reverse osmosis ornano-filtration, to dewater and concentrate the lithium product solution417 producing a product eluate with higher lithium tenor 419, whileproducing a recycle stream 420 suitable for use as make-up or as fresheluant 416. The optional membrane dewatering of the high tenor lithiumproduct would recycle a portion of the water used in the preparation ofthe eluant solution. Depending on the permeability of the membrane, aportion of the lithium could pass through the membrane without passingmultivalent brine components and become the lithium make-up for fresheluant.

The CCIX circuit 400 recovers greater than 97% of the lithium from thefeed brine and produces a lithium product eluate solution 342 having aconcentration 10- to 20-fold that of the feed brine with a 99.9%rejection of brine hardness ions. The production of this high puritylithium, directly from brine, without the need for extra rinse water, isan extremely cost effective process of obtaining commercially valuableand substantially pure lithium chloride, suitable for conversion tobattery grade carbonate or hydroxide.

The resin-based adsorbents for use in the CCIX lithium recovery unit 402may be prepared using large pore macroporous resin (plastic) beads thatare steeped repeatedly in sodium aluminate. Sodium aluminate ismanufactured by the dissolution of aluminum hydroxide in a caustic soda(NaOH) solution. The sodium aluminate gel is mixed with water to make asolution. As sodium aluminate is added to the resin bath tub, the pHjumps up and then as the reaction progresses, the pH will drop back toapproximately 5. Then more sodium aluminate is added, and is a “layer”deposited on the resin. After 4-6 times, it then goes through aneutralization step (making sure the sodium aluminate is out) and thenit takes a hot bath in a solution with lithium hydroxide at the properpH.

Turn back now to FIG. 2, after leaving the CCIX circuit 400, the lithiumchloride product stream 342 is passed to the lithium chloride conversioncircuit 500 where the lithium concentrated is further increased to inexcess of about 3,000 ppm. The lithium chloride conversion circuit 500removes selected remaining impurities and further concentrates lithiumin the lithium chloride product stream 342 before crystallization orelectrolysis.

The lithium chloride conversion circuit 500 initially removes anyremaining impurities 502, namely calcium, magnesium and boron, from thelithium chloride product stream 342. First, sodium hydroxide (causticsoda) is added in order to precipitate calcium and magnesium oxides fromthe lithium chloride product stream 342. The precipitated solids canproduce a Ca/Mg filter cake 504. Boron is then removed by passing thelithium chloride product stream 342 through a boron ion exchange (IX)circuit 528. The boron IX circuit is filled with an adsorbent thatpreferentially attracts boron, and divalent ions (essentially calciumand magnesium) are further removed in a divalent ion exchange (IX)circuit 530. This “polishing” step 502 ensures that these calcium,magnesium and boron contaminants do not end up in the lithium carbonateor lithium hydroxide crystals.

Then, the lithium chloride conversion circuit 500 uses a reverse osmosismembrane step 506 to initially concentrate lithium in the lithiumproduct stream 342 (target estimate from approximately 3,000 ppm to5,000 ppm). A triple effect evaporator 508 is then used to drive offwater content and further concentrate the lithium product stream. Thetriple effect evaporator 508 utilizes steam 510 from geothermaloperations and/or fuel boiler to operate. After processing through theevaporator 508, lithium concentration in the product stream is increasedfrom about 5,000 ppm to about 30,000 ppm.

The next steps in the lithium chloride conversion circuit 500 convertthe lithium chloride in solution to a lithium carbonate crystal. Sodiumcarbonate is added 512 to the lithium chloride product stream 342 toprecipitate lithium carbonate 514. The lithium carbonate 514 slurry issent to a centrifuge 516 to remove any moisture resulting in lithiumcarbonate cake. The lithium carbonate cake is re-dissolved 518, passedthrough a final purification or impurity removal step 520, andrecrystallized 522 with the addition of carbon dioxide 524. Thecrystallized lithium carbonate product is then suitable for packaging527.

Recovery of Lithium Hydroxide:

FIG. 3 illustrates another exemplary embodiment of the system andprocess 200 for recovery of lithium. After leaving the CCIX circuit 400,rather than using evaporation 508 exemplified in FIG. 2, a solventextraction process 702 concentrates lithium in the lithium chlorideproduct stream 342 using liquid-liquid separation, and after solventextraction 702 and electrolysis 708, the lithium is subsequentlycrystallized 710 into lithium hydroxide product 712.

Similar to the embodiment illustrated in FIG. 2, the lithium chlorideconversion circuit 500 first precipitates calcium and magnesium 502through the addition sodium hydroxide (caustic soda) resulting with aCa/Mg filter cake is produced 504. The pH of the lithium chlorideproduct stream 342 is lowered to about 2.5 in step 700 and then theacidified lithium chloride product stream 342 is introduced to thesolvent extraction step 702 in pulsed columns (tall vertical reactionvessels). The flow is scrubbed 704 and then stripped 706 with sulfuricacid producing a lithium sulfate product. The lithium sulfate productgoes through an electrolysis unit 708 producing lithium hydroxidecrystals 710. The lithium hydroxide crystals are then dried and packaged712.

Selective Recovery of Zinc, Manganese and Lithium:

Turning now to FIG. 4 illustrating yet another exemplary embodiment ofthe system and process 200 for recovery of lithium, the feed source isan incoming brine (e.g., a SSKGRA geothermal brine or the polished brine1038) (stream 1) and dilution water (stream 2). The incoming dilutionwater (stream 2) is mixed with filtrate (stream 25) from a Fe/Siprecipitate filter 322, then split, part (stream 21) being used as washto the Fe/Si precipitate filter 322 and the balance (stream 3) beingadded to the incoming brine (stream 1). The combined brine, dilutionwater and Fe/Si filtrate (stream 4) is pumped (stream 5) to the Fe/Siprecipitation stage 300A of the impurity removal circuit 300. Limestone310A (stream 169) is slurried with recycled barren brine (stream 168).The limestone/recycled barren brine slurry is added (stream 6) to thefirst set of reaction tanks 302 along with recycled precipitate seed(stream 18). Air is injected (stream 7/8) into the first tank 302 usinga blower 324. The iron is oxidized, and iron and silica are precipitatedaccording to the following stoichiometry:

2CaCO₃+2Fe²⁺+3H₂O+½O₂→2Fe(OH)₃+2CO₂+2Ca²⁺

3CaCO₃+3H₄SiO₄+2Fe(OH)₃→Ca₃Fe₂Si₃O₁₂+3CO₂+9H₂O

The spent air is vented (stream 9) from the first tanks 302, and theexit slurry (stream 10) is pumped (stream 11) to a thickener orclarifier 304 where flocculent (stream 12/13) is added and the solidsare settled out. The underflow from the clarifier 304 (stream 15) ispumped (stream 16) back to the first set of reaction tanks 302 as seed(stream 17) and (stream 19) to the filter feed tank 326. Precipitatefrom the Ca/Mg precipitation stage 540 of the impurity removal circuit502 is added (stream 73) and the combined slurry (stream 20) is filteredin the Fe/Si filter 322. The resulting Fe/Si filter cake is washed withdilution water (stream 22) and the washed filter cake 328 (stream 23)leaves the circuit 300. The filtrate (stream 24) is pump (stream 25) tothe dilution water tank 330.

The thickener overflow (stream 14) from the Fe/Si precipitation stage300A is combined with filtrate from a Zn/Mn precipitate filter 332(stream 45) in a feed tank 338 and the combined solution (stream 26) ispumped (stream 27) to the Zn/Mn precipitation stage 300B. Recycledprecipitate (stream 38) is added as seed and lime 312B (stream 173) isslaked with recycled barren solution (stream 172). Any gas released isvented (stream 174). The lime/recycled barren solution is added (stream28) to the second set of reaction tanks 306 to raise the pH to just over8 and precipitate zinc, manganese and lead oxides/hydroxides.

Any gas released is vented (stream 29) from the second tanks 306. Theexit slurry (stream 30) is pumped (stream 31) to a thickener orclarifier 308. Recycled solids from a subsequent polishing filter 334(stream 47) and flocculent (stream 32/33) are added and the precipitatedhydroxides are settled out. The thickener underflow (stream 35) ispumped (stream 36) to seed recycle (stream 37) and to the Zn/Mnprecipitate filter 332 (stream 39). The resulting Zn/Mn filter cake iswashed with process water (stream 41) and the washed filter cake 336(stream 43) leaves the circuit 300. The filtrate (stream 44) is pumped(stream 45) to the feed tank 338 ahead of the Zn/Mn precipitation stage300B. The thickener overflow (stream 34) is mixed with mother liquor(stream 134) from a first precipitation of lithium carbonate 514 and thecombined solution (stream 49) is pumped (stream 50) through thepolishing filter 334 to capture residual solids. The captured solids arebackwashed out (stream 46) and sent to the Zn/Mn precipitate thickener308.

The filtrate from the polishing filter 334 (stream 51) is mixed withspent eluant from the divalent IX circuit (stream 95) and hydrochloricacid 338 (stream 52/53) is added to reduce the pH to approximately 5.5.The resulting solution is cooled to approximately 185° F. in the mixingtank 340 and the cooled solution (stream 54) is passed through acontinuous counter-current ion exchange (CCIX) circuit 400 in which thelithium chloride is selectively captured onto the adsorbent. Theresulting barren solution (stream 55) is pumped (stream 48) to a holdingtank 343 from which it is distributed as follows:

to slurry the limestone to the Fe/Si precipitation stage 300A (stream167);

to slake the lime to the Zn/Mn precipitation stage 300B (stream 171);and

the balance (stream 165) is pumped away (stream 166) to be reinjectedinto the injection wells 320.

The loaded adsorbent is eluted with process water (stream 56) and theresulting eluate (stream 57) is pumped (stream 58) to a third set ofreaction tanks 532 for addition impurity removal 502, initially calciumand magnesium precipitation. Sodium hydroxide 554 (stream 179) isdissolved in process water (stream 181) and added (stream 59) to thetanks 532. Sodium carbonate 536 (stream 176) is dissolved in processwater (stream (177) pumped from a process water reservoir 538 and added(stream 60). A bleed of mother liquor (stream 156) from a secondprecipitation of lithium carbonate 524 and the spent regenerant from theboron IX circuit 528 (stream 192) are also treated in the Ca/Mgprecipitation section of the lithium chloride conversion circuit 500.The alkali earth ions (mainly Ca²⁺ and Mg²⁺) are precipitated accordingto the following stoichiometry:

Mg²⁺+2NaOH→2Na⁺+Mg(OH)₂

Ba²⁺+2NaOH→2Na⁺+Ba(OH)₂

Sr²⁺+2NaOH→2Na⁺+Sr(OH)₂

Ca²⁺+Na₂CO₃→2Na⁺+Ca(CO)₃

Any vapor evolved is vented (stream 61). The exit slurry (stream 62) ispumped (stream 63) to a thickener or clarifier 540, flocculent is added(stream 64/65) and the precipitate is settled out. The overflow (stream68) is pumped (stream 69) through a polishing filter 542. The underflow(stream 66) is pumped (stream 67) to a mixing tank 544 where it joinsthe solids (stream 70) from the polishing filter 542 and the combinedslurry (stream 72) is pumped (stream 73) back to the feed tank 326 aheadof the Fe/Si filter 322. The filtrate (stream 71) from the polishingfilter 542 is pumped (stream 74) to a feed tank 546 ahead of the boronIX circuit 528.

The filtrate (stream 75) from the Ca/Mg precipitation section of thelithium chloride conversion circuit 500 is pumped (stream 76) throughthe boron IX circuit 528 in which boron is extracted onto an ionexchange resin. The loaded resin is stripped with dilute hydrochloricacid (stream 78) that is made from concentrated hydrochloric acid(stream 185), process water (stream 186) and recycled eluate (stream80). The first 50% of the spent acid (stream 79), assumed to contain 80%of the boron eluted from the loaded resin, is mixed with similar spentacid from the subsequent divalent IX circuit 530 and recycled to thefeed to the CCIX circuit 400 (stream 94). The balance of the spent acid(stream 80) is recycled to the eluant make-up tank and recycled (stream77). The stripped resin is regenerated with dilute sodium hydroxide(stream 82) that is made from fresh sodium hydroxide (stream 188),process water (stream 189) and recycled regenerant (stream 84). Thefirst 50% of the spent regenerant (stream 83) is recycled to the Ca/Mgprecipitation section and the balance (stream 84) returns to aregenerant make-up tank 548 and is recycled (stream 81).

The boron-free product solution (stream 85) is pumped (stream 86)through divalent IX circuit 530 in which 99 percent of any remainingdivalent ions (essentially only Ca²⁺ and Mg²⁺) are captured by theresin. The loaded resin is stripped with dilute hydrochloric acid(stream 88) that is made from fresh hydrochloric acid (stream 182),process water (stream 184) and recycled spent acid (stream 93). Thefirst 50% of the spent acid (stream 91) joins the first half of thespent acid from the boron IX circuit 528 and the combined solution(stream 94) is sent back to the feed tank 340 ahead of the CCIX circuit400. The balance of the spent acid (stream 93) goes back to an eluantmake-up tank 550 and is recycled (stream 87). The stripped resin isconverted back to the sodium form by regeneration with dilute sodiumhydroxide (stream 89). The first 50% of the spent regenerant (stream92), assumed to have regenerated 80% of the resin, joins the spentregenerant (stream 83) from the boron ion exchange stage and goes back(stream 191) to the Ca/Mg precipitation section. The balance of thespent regenerant (stream 90) returns to the regenerant make-up tank 548.

The purified solution (stream 96) is pumped (stream 97) to a feed tank552 ahead of reverse osmosis 506 and mixed with wash centrate (stream131) from a first lithium carbonate centrifuge 554. The combinedsolution is split, part (stream 162) being used to dissolve sodiumcarbonate and the balance (stream 98) being pumped (stream 99) through areverse osmosis stage in which the water removal is manipulated to give95 percent saturation of lithium carbonate in the concentrate (stream101). The permeate goes to the process water reservoir (stream 100).

The partially concentrated solution from reverse osmosis 506 is furtherconcentrated in a triple-effect evaporation 508. The solution ex reverseosmosis (stream 101) is partly evaporated by heat exchanger 556 withincoming steam (stream 103). The steam condensate (stream 104) goes tothe process water reservoir 538, and the steam/liquid mixture to theheat exchanger 556 (stream 105) is separated in a knock-out vessel 558.The liquid phase (stream 109) passes through a pressure reduction 560(stream 110) and is further evaporated in a heat exchanger 562 withsteam (stream 106) from the first knock-out vessel 558. The condensate(stream 107) is pumped (stream 108) to the process water reservoir 538.The steam-liquid (stream 111) mixture is separated in a second knock-outvessel 564. The liquid (stream 115) goes through another pressurereduction step 566 (stream 116) and is evaporated further another heatexchanger 568 with steam (stream 112) from the second knock-out vessel564. The condensate (stream 113) is pumped (stream 114) to the processwater reservoir 538. The steam-liquid mixture (stream 117) is separatedin a third knock-out vessel 570. The steam (stream 118) is condensed(stream 119) by heat exchanger 572 with cooling water and pumped (stream120) to the process water reservoir 538.

The concentrated solution (stream 121) is pumped (stream 122) to thelithium carbonate crystallization section 514. Sodium carbonate 536(stream 175) is dissolved in dilute lithium solution (stream 163) fromthe feed tank 552 ahead of reverse osmosis 506 and added (stream123/124) to precipitate lithium carbonate. Any vapor evolved is vented(stream 125). The resulting slurry (stream 126) is pumped (stream 127)to a centrifuge in which the solution is removed, leaving a high solidscake. A small amount (stream 129) of process water is used to wash thesolids. The wash centrate (stream 130) is returned to the feed tankahead of reverse osmosis 506. The primary centrate (stream 133) isrecycled to a feed tank 336 ahead of the polishing filter 334 before theCCIX circuit 400.

The washed solids (stream 135) from the first centrifuge 554 are mixedwith wash (stream 136) and primary centrate (stream 153) from a secondcentrifuge 576. The resulting slurry (stream 137) is pumped to 15 barabs. (stream 138) and contacted with pressurized carbon dioxide 526(stream 139) to completely dissolve the lithium carbonate according tothe following stoichiometry:

Li₂CO₃+CO₂+H₂O→2Li⁺+2HCO₃ ⁻

The amount of primary centrate is manipulated to give 95 percentsaturation of lithium carbonate in the solution (stream 141) leaving theredissolution step 518. Any other species (Ca, Mg) remain as undissolvedcarbonates. The temperature of this step is held at 80° F. by heatexchange with chilled water 578 (stream 194 in, stream 193 out). Theresulting solution of lithium bicarbonate (stream 141) is filtered 580and the solid impurities leave the circuit 500 (stream 142). Thefiltrate (stream 143) is heated by live steam (stream 144) injection, todecompose the dissolved lithium bicarbonate to solid lithium carbonateand gaseous carbon dioxide:

2Li⁺+2HCO₃ ⁻→Li₂CO₃↓+CO₂↑+H₂O

The carbon dioxide formed (stream 145) is cooled by chiller 582 (stream157) and mixed with surplus carbon dioxide (stream 140) from there-dissolution step 518 and make-up carbon dioxide 528 (stream 158) in aknock-out vessel 586 from which the condensed water (stream 159) isremoved and the carbon dioxide (stream 160) is compressed 584 andreturned (stream 139) to the lithium re-dissolution step 518. The slurryof purified lithium carbonate (stream 146) is pumped (stream 147) to thesecond centrifuge 576 in which it is separated and washed with processwater (stream 148). The wash centrate (stream 152) is returned to there-dissolution step 518. The primary centrate (stream 150) is pumped(stream 151) back to the Ca/Mg precipitation section (stream 155) and tothe lithium re-dissolution step (stream 136). The washed solids (stream154) leave the circuit as the lithium carbonate product.

The condensate from the carbon dioxide knock-out vessel 586 (stream 159)and condensate from the carbon dioxide compressor 584 (stream 161) arecombined and sent (stream 195) to the process water reservoir 538. Thepermeate from the reverse osmosis 506 (stream 100) and the condensatesfrom the evaporation sequence 508 (streams 104, 108, 14) also go to theprocess water reservoir 538. Make-up water (stream 164) is added to theprocess water reservoir 538 if necessary to balance the followingrequirements for process water:

wash to the Zn/Mn precipitate filter 332 (stream 40);

eluate to the CCIX circuit 400 (stream 149);

centrifuge 554/576 wash water (streams 128/132); and

reagent make-up water (streams 178/181/183/187/190).

Selective Recovery of Zinc and Manganese:

FIG. 6 shows an illustrative example of mineral recovery as part of theinventive system and process 200 disclosed herein. After the impurityremoval circuit 300, the recovery of metals from the second filter cake316 is possible through a solvent extraction (SX) circuit 600. The SXcircuit leaches manganese and zinc from the filter cake with anapplication of an acid and then selectively strips the manganese andzinc using a solvent under different pH conditions. The resultingintermediate products are zinc sulfate liquor and manganese sulfateliquor, both of which can be sold as agricultural products, processedfurther by electrowinning into metallic form, or as feedstock toalternative products such as electrolytic manganese dioxide amongothers.

The SX circuit 600 begins with leaching 604 the second filter cake 316in a stirred, repulp reactor 602 with sulfuric acid (H₂SO₄) orhydrochloric acid (HCl) to reduce the pH down to about 2.5 (606). Areducing agent such as NaHS or SO₂ is added to the reactor 602 to ensureall of the manganese is in the +2 valence state for leaching. Thisimproves the kinetics and yield of the acid leach. The discharge fromthe leach reactor 602 will have its pH raised to approximately 5-6 withlime to precipitate any residual iron. The slurry will then be pumped toa polishing filter (not shown) followed by a pH adjustment toapproximately 2 to approximately 3. This becomes the Zn/Mn aqueous feedsolution 614 to the SX circuit 600.

The SX circuit 600 includes a zinc extraction stage 608, a zincscrubbing stage 610, and a zinc stripping stage 612. The Zn/Mn aqueousfeed solution 614 and an organic solvent 616 (e.g., Cytex 272) are fedin a counter-current manner into a first stage contactor in which thetwo phases are mixed and Zn is transferred from the aqueous phase intothe organic phase. After settling, the aqueous raffinate is separated618 and pH adjusted to between approximately 4.5 and approximately 5.5.After pH adjustment 620, the raffinate containing Mn 618 is sent forrecovery of a manganese sulfate product liquor 622.

From the zinc extraction stage 608, the zinc loaded solvent 624 is fedinto a second stage contactor where it is scrubbed with a suitableaqueous solution 626 to remove small amounts of impurities remaining.After settling in the zinc scrubbing stage 610, the scrub raffinate willbe recycled to an appropriate stream 628. The loaded solvent 630 is thenpumped to the zinc stripping stage 612 and fed into a third stagecontactor in which the Zn is stripped from the organic phase by asulfuric acid solution. The aqueous concentrated strip ZnSO4 productliquor 632 then goes for further processing depending on the desiredproduct form. The stripped solvent 616 is recycled back to the zincextraction stage 608.

The SX circuit 600 includes a manganese extraction stage 634, amanganese scrubbing stage 636, and a manganese stripping stage 638.Similar to the zinc SX circuit, the raffinate containing Mn 618 and anorganic solvent 648 (e.g., Cytex 272) are fed in a counter-currentmanner into a first stage contactor in which the two phases are mixedand Mn is transferred from the aqueous phase into the organic phase. Themanganese loaded solvent 640 is fed into a second stage contactor whereit is scrubbed with a suitable aqueous solution 642 to remove smallamounts of impurities remaining. After settling in the manganesescrubbing stage 636, the scrub raffinate will be recycled to anappropriate stream 644. The loaded solvent 646 is then pumped to themanganese stripping stage 638 and fed into a third stage contactor inwhich the Mn is stripped from the organic phase by a sulfuric acidsolution. The aqueous concentrated strip MnSO4 product liquor 622 thengoes for further processing depending on the desired product form. Thestripped solvent 648 is recycled back to the manganese extraction stage634.

It is to be understood that the terms “including”, “comprising”,“consisting” and grammatical variants thereof do not preclude theaddition of one or more components, features, steps, or integers orgroups thereof and that the terms are to be construed as specifyingcomponents, features, steps or integers.

If the specification or claims refer to “an additional” element, thatdoes not preclude there being more than one of the additional element.

It is to be understood that where the claims or specification refer to“a” or “an” element, such reference is not be construed that there isonly one of that element.

It is to be understood that where the specification states that acomponent, feature, structure, or characteristic “may”, “might”, “can”or “could” be included, that particular component, feature, structure,or characteristic is not required to be included.

Where applicable, although state diagrams, flow diagrams or both may beused to describe embodiments, the invention is not limited to thosediagrams or to the corresponding descriptions. For example, flow neednot move through each illustrated box or state, or in exactly the sameorder as illustrated and described.

Systems and processes of the instant disclosure may be implemented byperforming or completing manually, automatically, or a combinationthereof, selected steps or tasks.

The term “process” may refer to manners, means, techniques andprocedures for accomplishing a given task including, but not limited to,those manners, means, techniques and procedures either known to, orreadily developed from known manners, means, techniques and proceduresby practitioners of the art to which the invention belongs.

For purposes of the instant disclosure, the term “at least” followed bya number is used herein to denote the start of a range beginning withthat number (which may be a range having an upper limit or no upperlimit, depending on the variable being defined). For example, “at least1” means 1 or more than 1. The term “at most” followed by a number isused herein to denote the end of a range ending with that number (whichmay be a range having 1 or 0 as its lower limit, or a range having nolower limit, depending upon the variable being defined). For example,“at most 4” means 4 or less than 4, and “at most 40%” means 40% or lessthan 40%. Terms of approximation (e.g., “about”, “substantially”,“approximately”, etc.) should be interpreted according to their ordinaryand customary meanings as used in the associated art unless indicatedotherwise. Absent a specific definition and absent ordinary andcustomary usage in the associated art, such terms should be interpretedto be ±10% of the base value.

When, in this document, a range is given as “(a first number) to (asecond number)” or “(a first number)-(a second number)”, this means arange whose lower limit is the first number and whose upper limit is thesecond number. For example, 25 to 100 should be interpreted to mean arange whose lower limit is 25 and whose upper limit is 100.Additionally, it should be noted that where a range is given, everypossible subrange or interval within that range is also specificallyintended unless the context indicates to the contrary. For example, ifthe specification indicates a range of 25 to 100 such range is alsointended to include subranges such as 26-100, 27-100, etc., 25-99,25-98, etc., as well as any other possible combination of lower andupper values within the stated range, e.g., 33-47, 60-97, 41-45, 28-96,etc. Note that integer range values have been used in this paragraph forpurposes of illustration only and decimal and fractional values (e.g.,46.7-91.3) should also be understood to be intended as possible subrangeendpoints unless specifically excluded.

It should be noted that where reference is made herein to a processcomprising two or more defined steps, the defined steps can be carriedout in any order or simultaneously (except where context excludes thatpossibility), and the process can also include one or more other stepswhich are carried out before any of the defined steps, between two ofthe defined steps, or after all of the defined steps (except wherecontext excludes that possibility).

Still further, additional aspects of the instant invention may be foundin one or more appendices attached hereto and/or filed herewith, thedisclosures of which are incorporated herein by reference as if fullyset out at this point.

Thus, the invention is well adapted to carry out the objects and attainthe ends and advantages mentioned above as well as those inherenttherein. While the inventive concept has been described and illustratedherein by reference to certain illustrative embodiments in relation tothe drawings attached thereto, various changes and furthermodifications, apart from those shown or suggested herein, may be madetherein by those of ordinary skill in the art, without departing fromthe spirit of the inventive concept the scope of which is to bedetermined by the following claims.

1. A system for recovery of lithium from a lithium-containing brine,said system comprising: optionally, an impurity removal circuitconfigured for selectively removing silica, iron and certain metals fromsaid brine to produce a clarified or polished brine; a continuouscounter-current ion exchange circuit positioned downstream of saidimpurity removal circuit; said continuous counter-current ion exchangecircuit configured for selectively recovering lithium chloride from saidpolished brine; said continuous counter-current ion exchange circuitfurther configured for concentrating lithium chloride into a lithiumchloride solution; and a lithium chloride conversion circuit positioneddownstream of said continuous counter-current ion exchange circuit; saidlithium chloride conversion circuit configured for converting lithiumchloride in said lithium chloride solution to lithium carbonate orlithium hydroxide product.
 2. The system of claim 1 wherein said brineis a geothermal brine.
 3. The system of claim 1 wherein said impurityremoval circuit comprises: a first set of reaction tanks; a firstclarifier positioned downstream of said first reaction tanks; said firstclarifier configured to selectively remove precipitated silica and ironfrom said brine to form a substantially iron and silica free brine; asecond set of reaction tanks positioned downstream of said firstclarifier; a second clarifier positioned downstream of said secondreaction tanks; said second clarifier configure to selectively removeprecipitated metal oxides and/or hydroxides from said substantially ironand silica free brine to form a substantially zinc and manganese freebrine.
 4. The system of claim 1 further comprising a manganese and zincsolvent extraction circuit positioned downstream of said impurityremoval circuit and upstream of said continuous counter-current ionexchange circuit.
 5. The system of claim 4 wherein said manganese andzinc solvent extraction circuit comprises: a manganese zinc extractioncircuit comprising a zinc extraction stage having a first stagecontactor, a zinc scrubbing stage having a second stage contactor, and azinc stripping stage having a third stage contactor; and a manganesesolvent extraction circuit comprising a manganese extraction stagehaving a first stage contactor, a manganese scrubbing stage having asecond stage contactor, and a manganese stripping stage having a thirdstage contactor.
 6. The system of claim 1 wherein said continuouscounter-current ion exchange circuit comprises a continuouscounter-current ion exchange lithium extraction unit having a pluralityof ion exchange beds or columns containing a lithium selective adsorbentor resin.
 7. The system of claim 6 wherein said continuouscounter-current ion exchange lithium extraction unit further comprises aplurality of sequential, individual process zones.
 8. The system ofclaim 7 wherein each of said process zones said ion exchange beds orcolumns configured in parallel, in series, or in combinations ofparallel and series, flowing either in up flow or down flow modes. 9.The system of claim 8 wherein fluid flow through said continuouscounter-current ion exchange lithium extraction unit is controlled bypumping flow rates and a predetermined timing of a rotating or indexingmanifold valve system, whereby said ion exchange beds or columnscontinually cycle through said process zones.
 10. The system of claim 6wherein said lithium chloride selective absorbent or resin is amanufactured resin-based alumina imbibed adsorbent, a lithium aluminaintercalates adsorbent, an alumina imbibed ion exchange resin, or analumina-based adsorbent.
 11. The system of claim 1 wherein said lithiumchloride conversion circuit comprises: a third set of reaction tanks; athird clarifier positioned downstream of said third reaction tanks; saidthird clarifier configured to selectively remove precipitated calciumand magnesium from said lithium chloride solution to form asubstantially calcium and magnesium free brine; a boron ion exchangecircuit positioned downstream of said third clarifier; said boron ionexchange configured to selectively capture boron from said substantiallycalcium and magnesium free brine to form a substantially calcium,magnesium and/or boron free brine; and a monovalent or divalent ionexchange circuit positioned downstream of said boron ion exchangecircuit; said divalent ion exchange configured to selectively removingany remaining monovalent ions, divalent ions or a combination of bothfrom said substantially calcium, magnesium and/or boron free brine. 12.The system of claim 11 wherein said lithium chloride conversion circuitfurther comprising lithium crystallization circuit configured toselectively converting said lithium chloride in said substantiallycalcium, magnesium and/or boron free brine to lithium carbonate.
 13. Thesystem of claim 11 wherein said lithium chloride conversion circuitfurther comprising a solvent extraction and electrolysis circuitconfigured selectively converting said lithium chloride in saidsubstantially calcium, magnesium and/or boron free brine to lithiumhydroxide.
 14. A system for recovery of lithium from alithium-containing brine, said system comprising: a continuouscounter-current ion exchange circuit configured for selectivelyrecovering lithium chloride from said brine; said continuouscounter-current ion exchange circuit further configured forconcentrating lithium chloride into a lithium chloride solution; saidcontinuous counter-current ion exchange circuit comprising a continuouscounter-current ion exchange lithium extraction unit having a pluralityof ion exchange beds or columns containing a lithium selective adsorbentor resin; and said continuous counter-current ion exchange lithiumextraction unit further comprising a plurality of sequential, individualprocess zones.
 15. The system of claim 14 wherein said brine is ageothermal brine.
 16. The system of claim 14 further comprising animpurity removal circuit positioned upstream of said continuouscounter-current ion exchange circuit, and said impurity removal circuitconfigured for selectively removing silica, iron and certain metals fromsaid brine to produce a clarified or polished brine.
 17. The system ofclaim 16 wherein said impurity removal circuit comprises: a first set ofreaction tanks; a first clarifier positioned downstream of said firstreaction tanks; said first clarifier configured to selectively removeprecipitated silica and iron from said brine to form a substantiallyiron and silica free brine; a second set of reaction tanks positioneddownstream of said first clarifier; a second clarifier positioneddownstream of said second reaction tanks; said second clarifierconfigure to selectively remove precipitated metal oxides and/orhydroxides from said substantially iron and silica free brine to form asubstantially zinc and manganese free brine.
 18. The system of claim 14further comprising a manganese and zinc solvent extraction circuitpositioned downstream of said impurity removal circuit and upstream ofsaid continuous counter-current ion exchange circuit.
 19. The system ofclaim 18 wherein said manganese and zinc solvent extraction circuitcomprises: a manganese zinc extraction circuit comprising a zincextraction stage having a first stage contactor, a zinc scrubbing stagehaving a second stage contactor, and a zinc stripping stage having athird stage contactor; and a manganese solvent extraction circuitcomprising a manganese extraction stage having a first stage contactor,a manganese scrubbing stage having a second stage contactor, and amanganese stripping stage having a third stage contactor.
 20. The systemof claim 14 wherein said process zones comprise said ion exchange bedsor columns containing said lithium selective adsorbent or resin.
 21. Thesystem of claim 20 wherein said ion exchange beds or columns of saidprocess zones are configured in parallel, in series, or in combinationsof parallel and series, flowing either in up flow or down flow modes.22. The system of claim 21 wherein fluid flow through said continuouscounter-current ion exchange lithium extraction unit is controlled bypumping flow rates and a predetermined timing of a rotating or indexingmanifold valve system, whereby said ion exchange beds or columnscontinually cycle through said process zones.
 23. The system of claim 14wherein said lithium chloride selective absorbent or resin is amanufactured resin-based alumina imbibed adsorbent, a lithium aluminaintercalates adsorbent, an alumina imbibed ion exchange resin, or analumina-based adsorbent.
 24. The system of claim 14 further comprising alithium chloride conversion circuit positioned downstream of saidcontinuous counter-current ion exchange circuit; said lithium chlorideconversion circuit configured for converting lithium chloride in saidlithium chloride solution to lithium carbonate or lithium hydroxideproduct.
 25. The system of claim 24 wherein said lithium chlorideconversion circuit comprises: a third set of reaction tanks; a thirdclarifier positioned downstream of said third reaction tanks; said thirdclarifier configured to selectively remove precipitated calcium andmagnesium from said lithium chloride solution to form a substantiallycalcium and magnesium free brine; a boron ion exchange circuitpositioned downstream of said third clarifier; said boron ion exchangeconfigured to selectively capture boron from said substantially calciumand magnesium free brine to form a substantially calcium, magnesiumand/or boron free brine; and a divalent ion exchange circuit positioneddownstream of said boron ion exchange circuit; said divalent ionexchange configured to selectively removing any remaining divalent ionsfrom said substantially calcium, magnesium and/or boron free brine. 26.The system of claim 24 wherein said lithium chloride conversion circuitfurther comprising a crystallization circuit configured to selectivelyconverting said lithium chloride in said substantially calcium,magnesium and/or boron free brine to lithium carbonate.
 27. The systemof claim 24 wherein said lithium chloride conversion circuit furthercomprising a solvent extraction and electrolysis circuit configuredselectively converting said lithium chloride in said substantiallycalcium, magnesium and/or boron free brine to lithium hydroxide.